Basic Oxygen Process

2013 World Steel Association
s t e e l uni versi t y
Basic Oxygen Steelmaking Simulation, version 1.36 User Guide
1 Introduction and Disclaimer ..............................................................................3
2 About this Version...........................................................................................3
3 Introduction to Basic Oxygen Steelmaking.........................................................3
4 Simulation Objectives ......................................................................................4
5 Plant Layout and Description ............................................................................4
6 Simulation Options ..........................................................................................5
6.1 Simulation Mode............................................................................................................5
6.1.1 STANDALONE MODE.....................................................................................5
6.1.2 LINKED MODE.................................................................................................5
6.2 User Levels....................................................................................................................5
6.2.1 University Student Level ..................................................................................5
6.2.2 Steel Industry Works Technical Level .............................................................5
6.3 Simulation Speed......................................................................................................... 6
6.4 Target Steel Grade....................................................................................................... 6
7 Planning your Schedule ...................................................................................6
7.1 Composition...................................................................................................................7
7.2 Temperature..................................................................................................................7
7.2.1 Calculation of Liquidus Temperature.............................................................. 8
7.3 Stages of the Oxygen Blowing Process ...................................................................... 8
7.3.1 Silicon Oxidation Period.................................................................................. 8
7.3.2 Full Decarburization Period............................................................................. 8
7.3.3 Carbon Diffusion Period.................................................................................. 9
8 User Interface..................................................................................................9
8.1 Controls During Simulation.........................................................................................10
8.1.1 Make Additions (Key A)..................................................................................10
8.1.2 View Steel Composition vs. Time (Key C).....................................................10
8.1.3 View Event Log (Key E) ................................................................................. 11
8.1.4 View Melting Path (Key p).............................................................................. 11
8.1.5 View or Request Chemical Analysis (Key R) ................................................ 11
8.1.6 View Slag Composition vs. Time (Key S)...................................................... 11
8.1.7 Close Dialog Box(Key X)................................................................................ 12
8.2 Simulation Results....................................................................................................... 12
9 Underlying Scientific Relationships ................................................................. 12
9.1 Calculating Additions................................................................................................... 12
9.1.1 Elemental Additions........................................................................................ 13
9.1.2 Pickup of Other Elements .............................................................................. 13
9.1.3 Mixing Times................................................................................................... 14
9.2 Important Reactions .................................................................................................... 14
9.2.1 Phosphorus Partition Ratio............................................................................ 15
9.2.2 Dephosphorization Kinetics During Post-Blow Stir....................................... 15
9.2.3 Sulfur Partition Ratio...................................................................................... 16
9.2.4 Manganese Partition Ratio............................................................................. 16
10 Writing Heat and Mass Balances ..................................................................... 16
10.1 Introduction.................................................................................................................. 16
10.2 Mass Balance.............................................................................................................. 17
10.3 Heat Balance............................................................................................................... 17
10.3.1 Thermodynamic Functions and Units:........................................................... 17
10.3.2 Principles for the Establishment of Heat Balance.........................................18
10.3.3 Example of Application: Steel Heating by Aluminothermy........................... 20
11 Charge Calculation ........................................................................................ 21
11.1 Choice of Balance Equations...................................................................................... 21
11.2 Principle of Using the Simplex Method to Solve the Balance Equations ................. 22
11.3 How to Write the Balance Equations......................................................................... 23
11.3.1 Fe Balance..................................................................................................... 23
11.3.2 O Balance...................................................................................................... 23
11.3.3 Gas Balance.................................................................................................. 23
11.3.4 Balance of Slag Elements Other than Fe..................................................... 23
steeluniversity Basic Oxygen Steelmaking Simulation User Manual
2013 World Steel Association 2
11.3.5 Basicity Equation........................................................................................... 23
11.3.6 Energy Balance............................................................................................. 24
11.4 Numerical Application................................................................................................. 24
12 Bibliography .................................................................................................25

1 Introduction and Disclaimer
This document has been prepared as a user guide to the basic oxygen steelmaking (BOS)
simulation, available at http://www.steeluniversity.org/. The interactive simulation has
been designed as an educational and training tool for both students of ferrous metallurgy
and for steel industry employees.
The information contained both in this document and within the associated website is
provided in good faith but no warranty, representation, statement or undertaking is given
either regarding such information or regarding any information in any other website
connected with this website through any hypertext or other links (including any warranty,
representation, statement or undertaking that any information or the use of any such
information either in this website or any other website complies with any local or national
laws or the requirements of any regulatory or statutory bodies) and warranty, representation,
statement or undertaking whatsoever that may be implied by statute, custom or otherwise is
hereby expressly excluded. The use of any information in this document is entirely at the risk
of the user. Under no circumstances shall the World Steel Association or their partners be
liable for any costs, losses, expenses or damages (whether direct or indirect, consequential,
special, economic or financial including any losses of profits) whatsoever that may be incurred
through the use of any information contained in this document.
Nothing contained in this document shall be deemed to be either any advice of a technical or
financial nature to act or not to act in any way.
2 About this Version
Changes since version 1.0
- It is now possible for registered users to load simulation results from the Blast
Furnace Simulation.
3 Introduction to Basic Oxygen Steelmaking
Basic oxygen steelmaking (BOS) is the most widely used process for producing crude steel
from molten pig iron (hot metal). The process involves blowing oxygen through hot metal to
reduce its carbon content by oxidation. There exist many different types of furnaces, also
called converters since they are used to convert hot metal to steel, and these are generally
divided into top-blowing, bottom-blowing and mixed blowing.
Top-blowing through a vertical lance was invented in 1952-53 at Linz and Donawitz in Austria
and the process is known as LD (Linz Donawitz), or BOP (Basic Oxygen Process). Bottom-
blowing processes use, apart from oxygen, hydrocarbon gas (propane or natural gas) or fuel-
oil hydrocarbon that cools the refractory in the tuyere zone. These corresponding processes
are known as OBM (Oxygen Bottom-blowing Maxhtte), Q-BOP (Quick Basic Oxygen
Process) and LWS (Loire-Wendel-Sidelor). One of their advantages is a very efficient metal-
slag stirring throughout the oxygen blow.
Mixed blowing developed in the late 1970s is the latest step. A limited blowing of neutral gas
(argon or nitrogen) or oxygen through the vessel bottom of top-blown converters provides an
efficient stirring. The corresponding processes are known as LBE (Lance Bubbling
Equilibrium), LET (Lance Equilibrium Tuyeres), K-BOP (Kawasaki Basic Oxygen Process),
K-OBM (Kawasaki Oxygen Bottom-blowing Maxhtte) etc. and these facilities now equips
most of the top-blown converters.
Hot metal desulfurization is generally carried out prior to the hot metal being charged into the
furnace. Different fluxes are used for different levels of sulfur; for example lime, calcium
carbide and magnesium.
Hot metal dephosphorization was developed in Japan in the early 1980s. In this pretreatment
operation, most of the hot metal P is removed using oxidizing fluxes (mixtures of lime and
iron ore) in the hot metal ladle prior to charging in the converter. This treatment has so far
not been applied at all outside of Japan.
4 Simulation Objectives
The aim of the simulation is to take charge of a Basic Oxygen Furnace (BOF), treat the hot
metal by making necessary additions and blowing of oxygen, and tap the heat into the ladle at
the specified time, composition and temperature.
You should also aim to minimize the cost of the whole operation.
5 Plant Layout and Description

Figure 5-1: Screenshot showing the plant layout used in the simulation.
The plant in the simulation is laid out as shown in Figure 5-1. At the start of the simulation, an
animation shows how scrap metal and additives like lime and dolomite (according to the
user's choices) are first charged into the furnace. After the solid material has been charged the
hot metal is tapped from the transport ladle into the furnace. The simulation ends with a
summary screen when the steel has been tapped into the ladle.
Scrap & fluxes
Hot metal
charging ladle
Converter
Ladle
Oxygen lance
Slag pot
6 Simulation Options
6.1 Simulation Mode
The simulation can be run in one of either two modes:
Standalone mode
Linked mode
6.1.1 STANDALONE MODE
In this mode you will be able to select your user level, the grade of steel and other parameters.
6.1.2 LINKED MODE
Use the drop-down menu to view and select the available batches (Batch ID); the details will
be displayed below (see Figure 6-1). To access this feature you must be registered and logged
into the site.

Figure 6-1 Screenshot showing data loaded from previous process stage

6.2 User Levels
The simulation has been developed for use by two different user groups:
University students of metallurgy, materials science and other engineering disciplines
Steel industry works technical
6.2.1 UNIVERSITY STUDENT LEVEL
At this level the user will be expected to approach the problem scientifically, using the relevant
thermodynamic and kinetic theories to make decisions on the various processing options. For
example, the user should perform a full heat and mass balance calculation to determine the
amount of scrap and slag additions and the necessary total oxygen volume.
At this level the unmelted solids, e.g. scrap and iron ore, will be visible to the user.
6.2.2 STEEL INDUSTRY WORKS TECHNICAL LEVEL
At this level the user will also be expected to approach the problem scientifically. However, the
user will have to complete the simulation with a limited number of aids. For example, the
unmelted solids will not be visible at this level.
6.3 Simulation Speed
The simulation can be run at a range of different speeds between 1 and 32. The rate can be
changed at any time during the simulation. However, when important events take place the
simulation will automatically default to 1.
6.4 Target Steel Grade
The simulation includes a number of different steel grades to illustrate a range of different
processing options.
The general-purpose construction steel grade (CON) is a relatively undemanding grade
that requires minimal processing, and is therefore recommended for the novice user. Your
main job is to ensure that the carbon content is between 0.1 and 0.16%.
The TiNb ultra-low carbon steel (ULC), for automotive body parts, has a carbon
specification of less than 0.01%C with the aims to optimize formability. Your main priority
therefore is temperature control at the end of the blow to keep the temperature below
maximum whilst achieving the low target content.
The linepipe steel (LPS) for gas distribution is a very demanding grade as the
combination of high strength and high fracture toughness demands extremely low levels of
impurities (S, P, H, O and N) and inclusions. Only more experienced users are recommended
to attempt this grade.
The engineering steel (ENG) is a heat-treatable low alloy grade with a relatively high
carbon content. Choosing the correct starting temperature is imperative to achieve the target
temperature whilst maintaining the carbon content between 0.30 and 0.45%C.
Table 6-1: Maximum contents for the four target steel grades available in the simulation / wt-%.
Element CON ULC LPS ENG
C 0.16 0.01 0.08 0.45
Si 0.25 0.25 0.23 0.40
Mn 1.5 0.85 1.1 0.90
P 0.025 0.075 0.008 0.035
S 0.10 0.05 0.01 0.08
Cr 0.10 0.05 0.06 1.2
B 0.0005 0.005 0.005 0.005
Cu 0.15 0.08 0.06 0.35
Ni 0.15 0.08 0.05 0.30
Nb 0.05 0.03 0.018 0
Ti 0.01 0.035 0.01 0
V 0.01 0 0.01 0.01
Mo 0.04 0.01 0.01 0.30
Ca 0 0 0.005 0
Table 6-2: Aim tapping temperatures for the four target steel grades / C.
Minimum Maximum
CON 1630 1660
ULC 1665 1695
LPS 1655 1685
ENG 1655 1685

7 Planning your Schedule
Before you start the simulation, it is important that you plan ahead. The first thing to do is to
complete a heat and mass balance calculation to determine the amounts of hot metal, scrap,
iron ore, slag additions and total oxygen volume required to decarburize the hot metal to the
desired carbon content and temperature. You then need to think how to achieve the aim
values within the required time.
Table 7-1: Example Hot Metal and Tapping (Aim) Compositions for the Ultra-Low Carbon steel
grade. Carbon, silicon and phosphorus compositions must all be decreased, whereas
manganese can be left as is. Also, the temperature will have to be increased.
Hot Metal / wt% Tapping / wt% Difference / wt%
C 4.5 0.01 -4.49
Si 0.4 0.25 -0.15
Mn 0.5 0.85 +0.35
P 0.08 0.075 -0.005
Temperature 1350C 1680C +330C

7.1 Composition
Some additions will have to be made in order to meet the aim composition. Here are the key
questions you will need to answer
Which additive(s) can be used to achieve this?
How much additive (in kg) will be required?
Will this additive affect other elements too and if so, how much?
When should you make the addition?
How will the additions affect cost, steel composition and temperature?
Table 7-2: Compositions and costs of available additives.
Additive Composition Cost per
tonne
Hot Metal 4.5%C, 0.5%Mn, 0.4%Si, 0.08%P, 0.02%S + Fe bal. $185
Light scrap
0.05%C, 0.12%Mn, 0.015%P, 0.015%S, 0.06%O, 0.003%Ce,
0.26%Cr, 0.02%Cu, 0.14%Mo, 0.001%Nb, 0.4%Ni 0.001%Sn,
0.015%Ti, 0.005%V, 0.009%W + Fe bal.
$190
Heavy scrap
0.05%C, 0.12%Mn, 0.015%P, 0.015%S, 0.06%O, 0.003%Ce,
0.26%Cr, 0.02%Cu, 0.14%Mo, 0.001%Nb, 0.4%Ni, 0.001%Sn,
0.015%Ti, 0.005%V, 0.009%W + Fe bal.
$150
Iron Ore 99.1%FeO, 0.3%Al
2
O
3
, 0.5%CaO, 0.1%MgO, 0.001%P $85
Lime 94.9%CaO, 1.2%Al
2
O
3
, 1.8%MgO, 2.1%SiO
2
$85
Dolomite 59.5%CaO, 38.5%MgO, 2%SiO
2
$85

Table 7-3: Typical recovery rates for elements added (%).
Element C Si Mn P S Cr Al B Ni
Recovery rates 95 98 95 98 80 99 90 100 100
Element Nb Ti V Mo Ca N H O Ar
Recovery rates 100 90 100 100 15 40 100 100 100
Element As Ce Co Cu Mg Pb Sn W Zn
Recovery rates 100 100 100 100 100 100 100 100 100

7.2 Temperature
In order that the correct tapping temperature is achieved, it is important to consider the
effects of different additions on the steel temperature.
1. Under holding conditions, such as when stirring gas has been turned off and there is
no oxygen injection, the steel cools at around 1 to 2C min
-1
.
2. For most additions, each tonne (1000 kg) added results in an additional temperature
drop of about 5C.
3. Phosphorus and silicon oxidation is highly exothermic and produces about
26 MJ/tonne per 0.1% per tonne of hot metal oxidized, the equivalent of nearly
3 C/tonne per 0.1%.
4. Carbon oxidation is also exothermic and produces about 13 MJ/tonne per 0.1%
oxidized, the equivalent of about 1.4 C/tonne per 0.1%.
5. Increasing the hot metal or steel temperature requires 9.0 or 9.4 MJ/tonne,
respectively.
By carefully calculating the overall time from charging to tapping the BOF it should be
possible to estimate the temperature vs. time profile.
7.2.1 CALCULATION OF LIQUIDUS TEMPERATURE
It is imperative to prevent the steel bath temperature falling below the liquidus temperature
(i.e. the temperature at which the steel starts to solidify). The liquidus temperature, T
liq
, is
very dependent on composition and can be approximated from the following equations:
For %C < 0.5:
T
liq
(C) = 1537 - 73.1%C - 4%Mn - 14%Si - 45%S - 30%P - 1.5%Cr - 2.5%Al -
3.5%Ni - 4%V - 5%Mo 7-1
For 0.5 < %C < 4.4:
T
liq
(C) = 1531 61.5%C - 4%Mn - 14%Si - 45%S - 30%P - 1.5%Cr - 2.5%Al -
3.5%Ni - 4%V - 5%Mo 7-2
For %C > 4.4:
T
liq
(C) = 389 %C - 10.5 %Mn + 105 %Si + 140 %S + 128 %P - 506
7.3 Stages of the Oxygen Blowing Process
There are three typical reaction periods during BOP to consider; silicon oxidation, full
decarburization and carbon diffusion. These all have distinctly different reaction patterns. An
overview can be seen in Figure 7-1.
7.3.1 SILICON OXIDATION PERIOD
During the first third (approximately) of the blow most of the Si is oxidized along with some
Fe. A good practice is to increase the FeO content and get a good foaming slag at the very
beginning of the blow and then stabilize it by lowering the lance until the foam stops rising.
It is also during this period that most of the P and Mn are oxidized. The remainder of the
supplied oxygen reacts with carbon
7.3.2 FULL DECARBURIZATION PERIOD
Under normal conditions, all of the supplied oxygen reacts with carbon. However, if the lance
position is too high, a portion of the oxygen will instead oxidize Fe. On the other hand, when
the lance is too low, the previously formed FeO (and foaming slag) is reduced and the oxygen
released reacts with C.

Figure 7-1: Reaction rates for oxidation reactions in BOS.
7.3.3 CARBON DIFFUSION PERIOD
At the end of the blow when the carbon content is less than 0.8%C, the rate of decarburization
decreases substantially and is now increasingly limited by the diffusion of carbon in the steel.
An approximate equation for decarburization during period is shown in (remaining oxygen
will oxidize Fe):

( )
2
O
C %
15 . 0
98 . 0
C %
2
+
= A
V
7-3
where
A%C = change in carbon content in wt-%
%C = current carbon content in wt-%
2
O
V = oxygen supplied in m
3
/tonne
8 User Interface
This section describes the basic mechanics of running the simulation, e.g. how to move the
lance, how to make alloy additions, how to control oxygen flow, etc.
The underlying scientific relationships (chemistry, thermodynamics, reaction kinetics, etc.)
that you will need to use in order to calculate alloy amounts, process parameters, etc. are
presented in Section 9.
The common controls that are used include:
Stepper controls; used for selecting amounts, these have up and down arrows
which can be clicked on to increase or decrease the amount, or you can use the up and
down arrow on your keyboard once the control has been selected.
8.1 Controls During Simulation
Once the simulation begins, different sources of information can be displayed and/or
retrieved by pressing the relevant key given in the menu at the bottom left corner of the
screen. For you convenience, these keys are:
A: Make Additions
C: View Steel Composition v Time
E: Event Log
P: View Melting Path (%C v Time)
R: Review / Request Analysis
S: View Slag Composition v Time
X: Close dialogue boxes
8.1.1 MAKE ADDITIONS (KEY A)
During the hot metal conversion, you can make iron ore, lime and dolomite additions. Each of
these additives has a stepper control which is used to choose the amount to be added. By
default all steppers are initially set to zero. The unit cost of each additive is displayed, together
with the calculated cost for the selected amount.
TIP: Hover the cursor over the addition labels on the left for
information about their composition and typical recovery rates.

Figure 8-1: Screenshot illustrating the Addition interface. The boxed information shows the composition
of Iron Ore used in the simulation.
Note that that additions made do not result in instantaneous changes to the steel
composition, but take a finite time to dissolve. You can expect well-stirred additions made at
higher temperatures to dissolve fast while additions at lower temperatures with little or no
stirring will take many minutes to dissolve.
8.1.2 VIEW STEEL COMPOSITION VS. TIME (KEY C)
Pressing 'C' on the keyboard displays a diagram of how the steel composition has changed
over time. Elements displayed in this diagram include C, Si, Mn and P. This information
might be vital for determining which additions to make and when.
At Works Technical level you will not be able to see this information during the simulation.
However, it will be available at the summary screen so that it can be used as a part of a post-
mortem.
8.1.3 VIEW EVENT LOG (KEY E)
The event log keeps a chronological record of all the major processing steps, including
additions. This is useful for keeping track of what you have done so far during the simulation.
It is also very useful in helping you analyze your results at the end of the simulation, as the log
will often contain clues as to why you passed or failed the different criteria.
8.1.4 VIEW MELTING PATH (KEY P)
The melting path is a construction of information about carbon content, temperature and time
during the simulation superimposed on a C-Fe phase diagram. Each dot represents one
minute while the values of temperature and carbon content can be read out from the X- and
Y-axis.

Figure 8-2: Screenshot of the Melting Path diagram, in which the carbon content and temperature as a
function of time can be viewed.
Make sure that the melting path does not fall below the liquidus temperature, in which case
the heat might become partially or fully solidified. Solidification of the heat results, of course,
in failure.
8.1.5 VIEW OR REQUEST CHEMICAL ANALYSIS (KEY R)
You can view the most recent chemical analysis at any time by pressing key R. There is no cost
penalty for this. In most cases, the steel chemistry will have changed since the last analysis
was made. To initiate a new analysis, press the 'Take new sample' button. The analysis
costs $120, $40 for the actual analysis and $80 for the sublance consumable part. The results
take approximately 3 simulation minutes to arrive, e.g. about 22 real-world seconds if the
simulation rate is set to 8.
The time at which the sample was taken is displayed near the top of the dialog box. You must
always remember that the composition may have changed since the sample was taken.
8.1.6 VIEW SLAG COMPOSITION VS. TIME (KEY S)
Pressing 'S' on the keyboard displays a diagram of how the slag composition has changed over
time. Oxides displayed in this diagram include CaO, FeO
x
, MnO, MgO and SiO
2
. Primary use
of this diagram is to determine which slag additions to make and when. Also, by following the
FeO
x
content in the slag, it is possible to conclude how best to choose the oxygen blowing
pattern.
At Works Technical level you will not be able to see this information during the simulation.
However, it will be available at the summary screen so that it can be used as a part of a post-
mortem.
8.1.7 CLOSE DIALOG BOX(KEY X)
Press 'X' closes any of these dialogue boxes.
8.2 Simulation Results
As soon as tapping has been completed, the simulation will end and the results of the heat
displayed, together with the total operating costs, expressed as $ per tonne.

Figure 8-3: Screenshot of final results screen, in which the five criteria for success are displayed. Click
on the "Event Log" button to help you analyze your results.
9 Underlying Scientific Relationships
This section presents the key underlying scientific theories and relationships that are required
in order to successfully complete the simulation. In no way is it designed to be comprehensive
treatments of steelmaking theory and practice for this, the user is directed to other excellent
publications.
9.1 Calculating Additions
Scrap, slag and iron ore additions are made to the furnace for a variety of reasons
To adjust the liquid metal temperature
To adjust the liquid metal composition
To change the slag composition and thereby its properties
9.1.1 ELEMENTAL ADDITIONS
In the simplest case where a pure element is added, the amount of additive required, m
additive

is simply given by:

% 100
%
steel
additive
m X
m
A
= 9-1
where
X % A = required increase in wt-% X (i.e. %X
aim
- %X
current
)
m
steel
= mass of steel

Example
Suppose 250,000 kg of steel currently contains 0.01% Ni. How much elemental Ni must be
added to achieve an aim composition is 1.0% Ni?
kg 2,475
% 100
kg 000 , 250 )% 01 . 0 0 . 1 (
additive
=

= m 9-2
9.1.2 PICKUP OF OTHER ELEMENTS
When adding scrap it is also important to be aware of, and if necessary calculate, the effect of
elements other than iron on the overall steel composition. The new content of a given element
is calculated by Equation 9-3:
( )
steel scrap
steel steel scrap scrap
after steel,
100
% of rate recovery %
%
m m
X m X X m
X
+
+
= 9-3
where
i
X % = content of element i in wt-%
m
slag
= mass of slag in kg
m
steel
= mass of steel in kg

Example
Calculate the new content of carbon when 10,000 kg of Heavy Scrap is added to 250,000 kg
of Hot Metal.
Hot Metal contains 4.5%C (Table 7-2), Heavy Scrap contains 0.05%C (Table 7-2) and carbon
has got a 95% recovery rate (Table 7-3).

( )
C C % 33 . 4
kg 250,000 10,000kg % 100
% 5 . 4 250,000 5% 9 % 05 . 0 kg 10,000
%
after steel,
=
+
+
=
Evidently adding large amounts of scrap noticeably reduces the carbon content. However, it is
not possible to dilute the hot metal to the required carbon content only by adding scrap. Such
a large scrap addition would cause the whole melt to solidify in the furnace.
9.1.3 MIXING TIMES
Note that that additions made do not result in instantaneous changes to the steel
composition, but take a finite time to dissolve. In the simulation, be sure to allow sufficient
time for additions to melt and dissolve by observing the following trends:
Scrap additions dissolve faster than slag or iron ore additions
Blowing of oxygen accelerates the dissolution process since the oxidation reactions
that take place adds heat to the system
You can expect well-stirred additions made at higher temperatures to dissolve faster than
additions made at lower temperatures and/or with less stirring.
9.2 Important Reactions
The hot metal charge is refined by rapid oxidation reactions on contact with the injected
oxygen with the other elements present under conditions far removed from thermodynamic
equilibrium. The three most important reactions are:

(g) CO O [C]
2
= +
9-4

(g) CO O] [ [C] +
9-5

(g) CO O (g) CO
2 2
+
9-6
Post-combustion of CO into CO
2
(Equation 9-6) is only partial, i.e. only a part of the present
CO will oxidize into CO
2
. These gaseous reaction products (CO and CO
2
) are evacuated
through the exhaust hood. The ratio CO
2
/(CO+CO
2
) is called Post-Combustion Ratio (PCR).
Other important reactions that the simulation takes into account include:

2 2
SiO O [Si] = + 9-7

5 2 2
O P O
5
2
2[P] = + 9-8
MnO O
2
1
[Mn]
2
= + 9-9
FeO O
2
1
[Fe]
2
= + 9-10

3 2 2
O Fe O
2
3
2[Fe] = + 9-11
These oxides combine with previously charged oxides, e.g. lime and dolomite, to form a liquid
slag which floats on the surface of the metal bath. The composition of the slag is of utmost
importance since it controls many different properties, such as:
Sulfur partition ratio, L
S

Phosphorus partition ratio, L
P

Manganese partition ratio, L
Mn

Liquidus temperature of the slag
Each of these ratios indicate how the element will be distributed between the slag and the
steel, i.e. L
P
= 1 indicates that the level of phosphorus in the steel, [%P], is equal to the level in
the slag, (%P).
9.2.1 PHOSPHORUS PARTITION RATIO
Dephosphorization during the latter part of the basic oxygen steelmaking process is very
important because the conditions are favorable compared to other processes within primary
and secondary steelmaking. It is therefore critical to maintain a slag composition that
improves the phosphorus removal.
Figure 9-1 shows how the phosphorus partition ratio varies with different slag compositions.
Maintaining a high ratio is quite difficult since it exists only in a very narrow composition
range. Additionally, a temperature increase of 50 C leads to a decrease of L
P
with a factor of
1.6 at a basicity ratio (CaO/SiO
2
) of 3.

steel
slag
P
[%P]
(%P)
= L (at equilibrium) 9-12

Figure 9-1: L
P
in the system CaO-SiO
2
-FeO-2%P
2
O
5
-1.5%Al
2
O
3
-3%MnO-5%MgO at 1650 C
9.2.2 DEPHOSPHORIZATION KINETICS DURING POST-BLOW STIR
The rate at which the steel is dephosphorized during the post-blow stirring with e.g. nitrogen
or argon is controlled by
| | | |
eq
P
eq
%P P % %P P %
P %

= =
V
A
A
Q D
V
A
k
dt
d
c
| 9-13
where
k
c
= mass transfer coefficient of P in molten steel
A = cross sectional area at the slag-metal interface (m
2
)
V = steel volume (m
3
)
%P = P content in the steel at time t
%P
eq
= equilibrium P content at time t
| = empirical coefficient (~ 500 m
-1/2
)
D
p
= P diffusion coefficient in liquid steel (m
2
s
-1
)
Q = volumetric gas flow-rate across the interface (m
3
s
-1
)

9.2.3 SULFUR PARTITION RATIO
Although desulfurization is not a priority in BOS, there will still be a limited removal of S due
to slag/metal interface reactions. Figure 9-2 shows how the sulfur partition ratio varies with
slag composition. Please note that in the domain of liquid slags, L
S
is practically temperature
independent.

steel
slag
S
[%S]
(%S)

Figure 9-2: L
S
2
-FeO-2%P
2
O
5
-1.5%Al
2
O
3
9.2.4 MANGANESE PARTITION RATIO
Most of the manganese present in the hot metal will be oxidized during the first part of oxygen
blowing. Any remaining manganese may also be picked up by the slag or reverted back to the
steel due to oxidization/reduction reactions at the slag/metal interface.
The manganese partition ratio is slightly temperature dependant. An increased temperature
with 50 C leads to a decrease of L
Mn
with a factor of ~ 1.25.

steel
slag
Mn
[%Mn]
(%Mn)

Figure 9-3: L
Mn
2
-FeO-2%P
2
O
5
-1.5%Al
2
O
3
10 Writing Heat and Mass Balances
10.1 Introduction
Mass and heat balances are basic tools for:
charge computation
adjustment of the composition of certain entities (slag, etc.)
adjustment of steel temperature
diagnostic to evaluate materials and heat losses
10.2 Mass Balance
In a batch reactor, i.e. where vessel is emptied in between heats, the mass balance compares
materials inputs and outputs on the basis of their measured weights and analyses. The
difference between the two terms, if any, can be attributed to uncertainties on these
parameters, or to a poor identification of some of the inputs (refractory wear, slag carry-over,
etc.) or outputs (fumes, dusts, etc.):

) losses ( output input + = 10-1
One can consider:
global balances
balance for certain entities (gas, slag, etc.)
elementary balances (Fe, O
2
, CaO, etc.)
For instance, the balance for element X is written:
) losses ( %
100
1
%
100
1

+ =
j j i i
S
j
S E
i
E
X Q X Q 10-2
Depending on the context, this equation can be used for:
estimating loss terms
evaluating the amount
i
E
Q or
j
S
Q of an input or output
evaluating the composition
i
E
X % or
j
S
X % of an input or output
Establishing accurate mass balances is always the crucial first step to guarantee the validity of
the energy balance.
10.3 Heat Balance
10.3.1 THERMODYNAMIC FUNCTIONS AND UNITS:
The thermodynamic function measuring heat exchanges is enthalpy H. For a given material,
the enthalpy change as a function of temperature, in the absence of phase transformation, is
expressed from the heat capacity C
P
:
T C H H
T
T
p T T
d
2
1
1 2
=
}
10-3
The SI enthalpy unit is the Joule (J). Other practical units are:
calorie (cal) : 1 cal = 4.184 J
thermie (th) : 1 th = 10
6
cal
kilowatt-hour (kWh) : 1 kWh = 3.6 MJ = 0.86 th
A digest of basic data for Iron & Steelmaking applications, expressed as enthalpy variations of
various materials with temperature, phase transformations and chemical reactions is given in
the tables below.
10.3.2 PRINCIPLES FOR THE ESTABLISHMENT OF HEAT BALANCE
A practical method for expressing the heat balance consists of collecting the transformations
individually for each relevant chemical element, and summing-up at the end. For this
calculation, the second principle of the first law of thermodynamics is used: the heat of
reaction depends only on the initial and final states, and not on the intermediate states
through which the system may pass. It is thus sufficient to express the enthalpy of chemical
transformations at an arbitrary reference temperature (for instance 1600 C for a full charge
calculation, or the initial steel temperature for a simple temperature adjustment treatment)
and to express the enthalpy variations of reactants (respectively reaction products) between
their initial (respectively final) states and this reference temperature.
For instance, the process sketched below can be used:
0
2 1
= + A + A + A loss heat H H H
R
10-4

Figure 10-1: Calculation scheme for a heat balance.
The data in Tables 9.1 to 9.4 are used to compute the terms AH
1
, AH
2
and AH
R
. The values of
AH
R
are given for reactants and reaction products at 1600 C. They are as a first
approximation independent of temperature over a domain of several hundred degrees. Note
that these terms are positive for endothermic reactions, and negative for exothermic
reactions.
Depending on the application, this heat balance, coupled with the relevant materials balances,
can be used for:
charge diagnostic (e.g. evaluation of heat losses)
charge calculation (calculation of amounts of materials to be charged to obtain liquid
steel at a desired temperature)
temperature adjustment calculation (steel temperature variation for addition and
reaction of exothermic or endothermic materials). Note that the term AH
2
evaluated
from equation (4), represents the enthalpy variation of the output materials (liquid
steel, slag and possibly gas evolved during the operation) for the temperature
difference AT
steel
= T
f
- T
i
. The steel temperature change, using C
p
values in Table 9.1,
is then :
Heat losses
Reactions between
dissolved elements at
reference temperature
Input materials at initial
temperature
HR = sum of
enthalpies of
reactions
H2 = sum of enthalpies
of heating steel + slag +
gas +...
Output
materials at
final
temperature
H1 = sum of enthalpies of
decomposition + heating +
dissolution

slag steel
2
steel
04 . 2 82 . 0 Q Q
H
T
+
A
= A 10-5
where
AH2 = sum is of heating enthalpies in MJ
Q
steel
= mass of steel in tonnes
Q
slag
= mass of slag in tonnes

Table 10-1: Enthalpy values for materials as a function of temperature.

H (1400 C) - H (25 C)
/ MJ kg
-1

C
p
at 1400 C
/ kJ K
-1
kg
-1

Hot metal (liquid at 1400 C) 1.30 to 1.37 0.87

H (1600 C) H (25 C)
/ MJ kg
-1

C
p
at 1600 C
/ kJ K
-1
kg
-1
)
Low-alloyed steel (liq at 1600 C) 1.35 0.82
Refining slag (liq at 1600 C) 2.14 2.04
Iron ore Fe
2
O
3
(=> Fe
liq
+ O) 4.43
CaO 1.50 1.03
H (1600 C) - H (25 C) C
P
at 1600 C

/ MJ kg
-1
/ MJ m
-
/ kJ K
-1
kg
-1
/ kJ K
-1
m
-

Ar 0.82 1.46 0.53 0.93
CO 1.86 2.33 1.28 1.61
CO
2
1.90 3.78 1.36 2.71
N
2
1.84 2.30 1.28 0.95
O
2
1.70 2.43 1.17 1.68

Table 10-2: Enthalpy of oxidation reactions for various elements.
Element X to
Oxide XnOm
Heating from
25 to 1600 C +
dissolution
Cp element X at
1600 C
Oxidation X at
1600 C by
dissolved O
Oxidation X at
1600 C by O2
gas at 25 C
Amount O2
/ MJ kg
-1
/ kJ K
-1
kg
-1
/ MJ kg
-1
/ MJ kg
-1
/ kg / m
3

C in CO 4.56
*
to 6.0
**
2.025 -1.93
*
to -3.37
**
-9.4
*
to -10.84
**
1.33 0.93
C in CO2
4.56
*
to 6.0
**
2.025 -15.35
*
to -16.79
**

-30.35
*
to -
31.79
**

2.67 1.87
Al in Al2O3 - 0.17 1.175 - 22.32 - 27.32 0.89 0.62
Cr in Cr2O3 1.37 0.95 - 7.76 - 10.36 0.46 0.32
Fe in "FeO" liq 1.35 0.82 - 2.49 - 4.10 0.29 0.20
Fe in Fe2O3 1.35 0.82 - 4.06 - 6.48 0.43 0.30
Mn in MnO 1.53 0.835 - 5.34 - 6.97 0.29 0.20
P in C3P
***
- 0.14 0.61 - 23.8 - 31.05 1.29 0.90
Si in C2S
***
- 1.43 0.91 - 24.4 - 29.35 1.14 0.80
(
*
) in liquid steel
(
**
) in hot metal
(
***
) to form 3 CaO-P
2
O
5
and 2 CaO-SiO
2
with necessary CaO taken at 1600 C
Table 10-3: Reactions of oxygen dissolution in liquid steel at 1600 C (MJ/kg O
2
).
From O
2
gas
at 25 C
From FeO
x
in slag
at 1600 C
From very stable oxides
at 1600 C
- 5.62 8.7 18

Table 10-4: Enthalpy of decomposition of ferroalloys at 25C (MJ/kg alloy).
High C
Ferro-Cr
(64%Cr
5%C)
Refined
Ferro-Cr
(73%Cr
0.5%C)
High C
Ferro-Mn
(78%Mn
7%C)
Refined
Ferro-Mn
(80%Mn
1.5%C)
Ferro-
Silicon
(75%Si)
Ferro-
Silicon
(50%Si)
Silico-
Manganese
(35%Si)
0.11 - 0.025 0.10 0.075 0.37 0.70 0.71

10.3.3 EXAMPLE OF APPLICATION: STEEL HEATING BY ALUMINOTHERMY
Take the calculation of the change in steel temperature as an example of a heat and mass
balance. Initially at 1620 C, what will the steel temperature be after the addition of 1 kg Al (+
O
2
gas) per tonne of steel?
Applying the heat balance shown in Equation 10-4 provides the necessary parameters.
The materials balance indicates that 0.89 kg O
2
are necessary per kg Al, and that 1.89 kg Al
2
O
3

are formed (see Table 10-2).
1. Calculation of AH
1
: - 5.13 MJ including:
a. Heating and dissolution of 1 kg Al:
i. - 0.17 MJ (heating at 1600 C + dissolution, see Table 10-2)
ii. + 1.175.10
-3
20 (heating from 1600 to 1620 C)
b. Heating and dissolution of 0.89 kg O
2
:
c. - 5.620.89 MJ (heating at 1600 C + dissolution, see Table 10-3)
d. +1.17.10
-3
200.89 (heating from 1600 to 1620 C)
2. Calculation of AH
R
: -22.32 MJ (see Table 10-2)
3. Thus, AH
2
= - (AH
1
+AH
R
) = 27.45 MJ
The corresponding temperature change for 1 tonne of steel, taking into account a typical slag
weight of 20 kg/tonne (including formed Al
2
O
3
) and neglecting heat losses is:
C 31.9
020 . 0 04 . 2 82 . 0
45 . 27
steel
=
+
= AT
If the reaction takes place using dissolved oxygen instead of gaseous oxygen, it is necessary to
subtract from AH
1
the enthalpy of dissolution of oxygen, i.e. (-5.620.89 MJ/kg Al). The
temperature change is then:
C 1 . 6 2
020 . 0 04 . 2 82 . 0
89 . 0 62 . 5 45 . 27
steel
=
+

= AT
If the reaction takes place using oxygen resulting from the reduction of iron oxides in the slag,
it is necessary to add to this last value of AH
1
the enthalpy of decomposition of FeO
x
, i.e.
(8.70.89 MJ/kg Al). In this case, the temperature change would be:
C 1 . 17
020 . 0 04 . 2 82 . 0
89 . 0 7 . 8 89 . 0 62 . 5 45 . 27
steel
=
+

= AT
11 Charge Calculation
11.1 Choice of Balance Equations
The reaction products between hot metal and oxygen enter either the slag (Fe, Si, Mn, P, Cr
etc.) or the gas (C as CO and CO2) phase. The distribution of elements between liquid metal,
slag and gas depends on the amount of blown oxygen and on the conditions of contact
between hot metal and oxygen. The blowing conditions will influence:
Gas composition; post-combustion ratio PCR=CO
2
/(CO+CO
2
) where CO and CO
2
are
volumetric fractions.
Oxidation degree of Fe in the slag Fe
3+
/(Fe
2+
+ Fe
3+
). In top blowing, this ratio is
about 0.3 which corresponds to a mass ratio O
linked
to Fe/Fe
oxidized
= 0.33.
In addition, it is necessary to impose a constraint on the amount of oxidized Fe, usually
through a fixed value of the slag iron content. For stainless steels, oxidation of Cr is
considered, usually fixed through the oxygen decarburization yield.
In this simplified system, it is clear that for a steel of given composition, and once the three
discussed parameters are fixed (gas composition, oxidation degree and amount of oxidize Fe),
4 equations are necessary in order to evaluate the amounts of oxygen, liquid steel, slag and gas
corresponding to the treatment of a given amount of hot metal (or to produce a given amount
of steel). These equations are the balances of Fe, O, gas, and slag elements other than Fe (Si,
Mn and P). It can easily be shown that these equations are independent.
Any additional constraint will require an additional input variable (or the release of one of the
previous constraints). This is the case for typical industrial conditions:
The steel temperature is fixed. This constraint requires charging an endothermic
(scrap, ore, etc.) or exothermic (ferrosilicon, coal, etc.) agent.
Burnt lime addition for desired slag properties. This constraint can be expressed as an
additional imposition on slag composition (CaO content, or basicity-ratio CaO/SiO
2

or (CaO+MgO)/(SiO
2
+P
2
O
5
), or imposition of a burnt lime rate equation.
Fixation of the slag MgO content for lining protection. An independent MgO input is
necessary, for instance as dolomitic lime.
Table 11-1: Input and Output material from the Basic Oxygen Steelmaking Process.
Input Hot metal
Weight fixed (or unknown) (P
Fte
), composition and temperature
fixed
Scrap or Ore Weight unknown (P
Fer
or P
M
), composition and temperature fixed
Burnt lime Weight unknown (P
Chx
Oxygen Weight unknown (P
O
Output Liquid steel
Weight unknown (or fixed) (P
A
), composition and temperature
fixed
Slag
Weight unknown (P
L
), temperature fixed
Iron oxide and oxidation degree fixed (=> %Fe
L
, (%O
Fe
)
L
)
Complete composition will be computed from elementary
balances (Si, P, etc.)
Gas
Weight unknown (P
G
)
Average temperature and post-combustion ratio (PCR) fixed

Thus, a typical charge with the minimum amount of required materials has 6 unknowns and
requires 6 balance equations:
Fe balance
O balance
Gas balance
Balance of slag elements other than Fe
Basicity equation balance
Energy balance
11.2 Principle of Using the Simplex Method to Solve the Balance
Equations
In general, more materials than strictly necessary are available to make-up the charge
(various scrap qualities, ferroalloys, etc.). A practical way to compute the optimal charge
(minimal cost for a given steel grade) is to use the Simplex Algorithm which is a minimization
of the objective function charge cost z=f(c,P), a linear equation in terms of weights of the
various materials:

j
j
j
P c z =
11-1
Where
P
j
= weights of the various concerned materials (hot metal, scraps, etc., slag,
gas)
c
j
= cost including costs linked to their use, and possibly disposal costs (slag) or
valorization (gas)

The variables P
j
are submitted to the balances constraints, as well as other possible
constraints of materials availability, analytical limits, etc.:
{ } m i b P a
i j
n
j
ij
,..., 1 , ,
1
= > = s
=
11-2
Among the materials availability constraints, we may impose maximum or minimum weights
of certain materials (e.g. provision of a minimal amount of ore for final temperature
adjustment), or of certain materials assemblies (e.g. maximal capacity in weight and volume
of the scrap boxes), impose the weight of certain materials (e.g. solid iron, internal scrap).
Among analytical limits constraints, we may impose a maximal steel Cu (or other tramp
elements) content, the slag MgO content for lining protection, etc.
The possibility, with the Simplex Method, to impose arbitrarily the weight of certain
materials, offers the advantage of using the same calculation module for charge calculation
(the weight of liquid steel is fixed and that of hot metal and other charge materials are
unknown), and for heat diagnostic calculations (the charged materials are known and the
theoretical steel weight is computed, along with actual materials and heat losses).
11.3 How to Write the Balance Equations
The equations are written here for the standard charge with minimal number of materials.
The transposition to a higher number of available materials is direct.
11.3.1 FE BALANCE
| | | |
L L A A M M Fer Fer Fte Fte
Fe % Fe % Fe % Fe % Fe % P P P P P + = + + 11-3
11.3.2 O BALANCE
The amounts of oxygen used for the oxidation of the various elements C, Mn, P, Si are
computed on the basis of the amounts of these elements oxidized, Q
C
, Q
Mn
, Q
P
and Q
Si
.
| |
A A Fer Fer Fte Fte C
C % C % C % 01 . 0 P P P Q + = 11-4
(and similarly for Mn, P and Si)
Taking into account the amount of oxygen used for oxidizing Fe computed from the slag
composition, and the amount of dissolved oxygen in the steel, the oxygen balance is:

A A L M Fe Si P
Mn C M M O
O % 01 . 0 ) O (% 01 . 0
28
32
62
80
55
16
12
32
) 1 (
12
16
O % 01 . 0
P P Q Q
Q Q PCR PCR P P
+ + + +
+
(
+ = +
11-5
11.3.3 GAS BALANCE

C G
) (
12
44
) 1 (
12
28
Q TCS TCS P
(
+ = 11-6
When using a stirring gas (Ar, N
2
, etc.), it is necessary to add P
Ar
, P
N2
, etc.
11.3.4 BALANCE OF SLAG ELEMENTS OTHER THAN FE

| |
L L Fe L
Chx Chx Si P Mn
) O (% Fe % 100 01 . 0
CaO % 01 . 0
28
60
62
142
55
71
P
P Q Q Q
=
+ + +
11-7
11.3.5 BASICITY EQUATION
If, for instance, the basicity ratio v = %CaO/%SiO
2
is imposed:

Si Chx Chx
28
60
CaO % 01 . 0 Q v P = 11-8
11.3.6 ENERGY BALANCE
We use Equation 10-4 of section 10.3 Heat Balance, taking 1600 C for reference so that the
data of Tables 10-1 to -10.4 can be used simply. Note that in these tables, weights are in kg
and enthalpy terms in MJ or kJ:
Step 1
The charged materials are brought from their initial state to that of elements dissolved in
liquid metal at 1600 C (except burnt lime which is simply heated)
AH1 = 0.00087 (1600-T
Fte
) P
Fte
(heating hot metal - see Table 10-1-)

+1.35 P
Fer
+4.43 P
M
(heating and dissoloving scrap and ore - see Table 10-1-)
+1.5 P
Chx
(heating burnt lime - see Table 10-1-)
-5.62 P
O
(heating and dissolving oxygen - see Table 10-3-)

Also use data from Table 10-4 and the first column of Table 10-2 if ferroalloys are being
charged.
Step 2
Enthalpy of reactions between dissolved elements at 1600 C (Table 10-2).

| |
L L Si P Mn
C 2
Fe % 0296 . 0 4 . 24 8 . 23 34 . 5
79 . 16 ) 1 ( 37 . 3
P Q Q Q
Q PCR PCR H

= A
11-9
Step 3
Steel, slag and gas are brought to their final temperature.
AH3 = 0.00082 (T
A
-1600) P
A
(T
steel
- see Table 10-1)
+ 0.00204 (T
L
-1600) P
L
(T
slag
- see Table 10-1)
+[{0.00128 (T
G
-1600)} (1-PCR)+{0.00136 (T
G
-1600)} PCR] Q
C

(T
gas
for CO + CO2 - see Table 10-1)

Add the following respective term(s) if argon and/or nitrogen stirring gas are used:
+{0.82+0.00053 (T
G
-1600)} P
Ar
+{1.84+0.00128 (T
G
-1600)} P
N2

Table 11-2: Starting values for the heat and mass balance.
Hot metal composition 4.5 %C, 0.5 %Mn, 0.08 %P, 0.4 %Si (that is 94.52 %Fe) at 1350 C.
Scrap composition 100 %Fe. No ore.
Burnt lime 100 %CaO.
Liquid steel composition 0.05 %C, 0.12 %Mn, 0.01 %P (that is 99.73 %Fe) at 1650 C.
Slag %CaO/%SiO
2
=4, oxidized Fe content 18% at 1650 C.
Gas PCR=0.08 extracted at an average temperature of 1500 C.
Heat losses 65 MJ/t steel.

11.4 Numerical Application
The first step in making a charge calculation for 1 tonne steel is to calculate the amounts of
oxidized C, Mn, P and Si:
Q
C
= 0.045 P
Fte
-0.5
Q
Mn
= 0.005 P
Fte
-1.2
Q
P
= 0.0008 P
Fte
-0.1
Q
Si
= 0.004 P
Fte

Then, all 6 heat and mass balance equations are calculated according to Table 11-3:
Table 11-3: Heat and Mass balance end equations.
Fe balance 30 . 997 18 . 0 9452 . 0
L Fer Fte
= + P P P
O balance 098 . 1 0544 . 0 0718 . 0
L O Fte
= + + P P P
Gas balance 22 . 1 1098 . 0
G Fte
= P P
Balance of
slag
elements
other than
Fe
778 . 1 7606 . 0 0169 . 0
L Chx Fte
= + P P P
Slag
basicity
0 0343 . 0
Chx Fte
= P P
Energy
balance
2 . 117 3462 . 0 62 . 5 5 . 1 35 . 1 1287 . 0
L O Chx Fer Fte
= + + P P P P P

Finally, the masses are calculated:
P
Fte
= 885.3 kg
P
Fer
= 171.6 kg
P
Chx
= 30.4 kg
P
O
= 65.6 kg
P
A
= 1000 kg
P
L
= 57.2 kg
P
G
= 96.0 kg
12 Bibliography
- AISE, The Making, Shaping and Treating of Steel, Steelmaking and Refining Volume,
AISE, 1998, ISBN 0-930767-02-0.
- Turkdogan, ET, Fundamentals of Steelmaking, The Institute of Materials, 1996, ISBN 1
86125 004 5.

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